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Cited by 217

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Redox-Controlled Polymerization of Lactide Catalyzed by Bis(imino)pyridine Iron Bis(alkoxide) Complexes

Biernesser, Ashley B., Li, Bo, Byers, Jeffery A.·2013·Journal of the American Chemical Society
DOI 10.1021/ja407920d
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Abstract

Bis(imino)pyridine iron bis(alkoxide) complexes have been synthesized and utilized in the polymerization of (rac)-lactide. The activities of the catalysts were particularly sensitive to the identity of the initiating alkoxide with more electron-donating alkoxides resulting in faster polymerization rates. The reaction displayed characteristics of a living polymerization with production of polymers that exhibited low molecular weight distributions, linear relationships between molecular weight and conversion, and polymer growth observed for up to fifteen sequential additions of lactide monomer to the polymerization reaction. Mechanistic experiments revealed that iron bis(aryloxide) catalysts initiate polymerization with one alkoxide ligand, while iron bis(alkylalkoxide) catalysts initiate polymerization with both alkoxide ligands. Oxidation of an iron(II) catalyst precursor lead to a cationic iron(III) bis-alkoxide complex that was completely inactive toward lactide polymerization. When redox reactions were carried out during lactide polymerization, catalysis could be switched off and turned back on upon oxidation and reduction of the iron catalyst, respectively.

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Cited by

Metadata

Authors
Biernesser, A. B., Li, B., & Byers, J. A.
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2013-10-23
Volume
135
Issue
44
Pages
16553-16560
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/ja407920d
OpenAlex
W2331143715
Cited by
217
References
7
FWCI
6.35
Type
journal article
Language
en
Open access
closed

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